CN101252208B - Stacking nonaqueous electrolytes battery and manufacturing method thereof and stacking equipment - Google Patents
Stacking nonaqueous electrolytes battery and manufacturing method thereof and stacking equipment Download PDFInfo
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- CN101252208B CN101252208B CN2008100804820A CN200810080482A CN101252208B CN 101252208 B CN101252208 B CN 101252208B CN 2008100804820 A CN2008100804820 A CN 2008100804820A CN 200810080482 A CN200810080482 A CN 200810080482A CN 101252208 B CN101252208 B CN 101252208B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
- H01M10/0404—Machines for assembling batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/005—Devices for making primary cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/188—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
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Abstract
The invention provides a pile non-aqueous electrolyte battery, method for producing the battery and pile equipment of the battery. The pile non-aqueous electrolyte battery comprises multiple alternate pile electrode body, each of which comprises an anode and cathode overlapped through a partition. The partition has an edge part upraising along the edge part of one of the anode and cathode. The upraising edge parts of multiple partitions are overlapped with each other.
Description
Technical field
The present invention relates to stacking nonaqueous electrolytes battery and manufacture method thereof and stack equipment.Particularly, the present invention relates to by preventing that electrode from departing from stacking nonaqueous electrolytes battery and manufacture method thereof that improves its battery quality and performance in its suitable position and the stack equipment that is used for it when the stacked electrodes.
Background technology
As electronic equipment, for example mobile phone and notebook personal computer further tended to the development of wirelessization and portability in recent years, and the portable electric appts that thickness, size and weight reduce is developed by adjoining land.In addition, because the variation of type and function, their power consumption is increasing, and this needs battery to have higher capacity and the lighter weight energy as them.Therefore, in order to satisfy this requirement, and propose stacking nonaqueous electrolytes battery, at this wherein, comprised the various types of lithium rechargeable batteries that utilize the doped lithium ion that mixes/go.
In some lithium rechargeable battery, in order to obtain the thickness that reduces them, adopted and piled up type, wherein a plurality of anodes and negative electrode alternately pile up by spacer.In such battery, on a part, on two surfaces of anode collector 1b, form anode 1 with anode active material layers 1a, relative by spacer 3 with the negative electrode 2 that formation on two surfaces of cathode current collector 2b has cathode active material bed of material 2a, negative electrode 2 is greater than anode 1, and the length of spacer 3 is equal to, or greater than the length of negative electrode 2, shown in Figure 1A.In this structure, lithium ion passes spacer 3 chargings and discharge usually.
Yet, when anode 1 during, shown in Figure 1B, produce the ion that flows on directly with respect to the part of negative electrode 2 by spacer 3 at anode 1 greater than spacer 3 and therefore with respect to negative electrode 2, shown in the dotted line among the figure, in battery, cause the problem of for example short circuit and unusual heating.In addition, shown in Fig. 1 C, when anode 1 during not only greater than spacer 3 but also greater than negative electrode 2, lithium 4 is deposited on the marginal portion of negative electrode 2, and forms the ingotism thing, thereby causes short circuit.
Therefore, because any onely in anode 1, negative electrode 2 and the spacer 3 depart from the quality that all can influence battery greatly, thus need prevent anode 1 and negative electrode 2 during the manufacturing of battery or when being impacted afterwards since the inside battery element depart from that caused the two is directly opposite one another.
Therefore, proposed closed type sheet lithium battery, for example Japanese unexamined patent discloses the battery that 10-172565 number (calling " patent documentation 1 " in the following text) disclosed.In this battery, anode and negative electrode are loaded in bag shape spacer one of at least, and weld the marginal portion in this strip-like separator, and pile up as shown in Figure 2.Should be noted in the discussion above that in Fig. 2, piled up a plurality of anodes 1 and negative electrode 2, and illustrate by the packaging material that omit battery.
In addition, except battery with structure that patent documentation 1 disclosed, these batteries have for example also been proposed: have the battery that spiral twines the longitudinal cross-section structure of piling up, each all has the electrode body that wherein piles up 4 by spacer 3 stacked anode 1 and negative electrode 2, twine by another sheet spacer 3 spirals simultaneously, as shown in Figure 3; And the battery with folding longitudinal cross-section structure, wherein anode 1 and negative electrode 2 alternately insert in the space of spacer 3 of zigzag fold, as shown in Figure 4.
Summary of the invention
Yet, in the battery that patent documentation 1 is disclosed, wherein anode and negative electrode are packed into one of at least in the banded spacer, the water-tight equipment that need have the costliness of high position precision, has very little welding surplus so that guarantee at each edge of spacer, for example about 3mm to 4mm has increased manufacturing cost thus.In addition, because the welding surplus, electrode can not form very big size, and this has limited the increase of battery capacity.
In addition, have spiral twine pile up or the above-mentioned battery of folding longitudinal cross-section structure in, each electrode inserts between the spacer with certain interval, thus electrode only is held by the contact force from vertical adjacent electrode, for example shown in Fig. 5 A and the 5B.This can become flexible when applying impact and remain on its locational electrode, and causes that electrode departs from from its correct position, weakens the quality of battery probably.In addition, for these batteries, spacer 3 must be folding in special mode, and this must need expensive equipment.
In addition, in the simple structure that anode/cathode and spacer alternately pile up respectively, foreign substance may enter from the interface between spacer and the anode/cathode, and this also hinders cell reaction probably and weakens the quality and the safety of battery.
Therefore, be desirable to provide a kind of stacking nonaqueous electrolytes battery with better battery quality and performance, and manufacture method and stack equipment.
According to a first aspect of the invention, provide a kind of stacking nonaqueous electrolytes battery, it comprises a plurality of anode and negative electrodes that alternately pile up and isolated by spacer.Spacer has the marginal portion of raising along the marginal portion of one of anode and negative electrode.The marginal portion that this of a plurality of spacers raised overlaps each other.
According to a second aspect of the invention, provide a kind of method of making stacking nonaqueous electrolytes battery, comprise the steps: to pile up anode or negative electrode and spacer, thereby raise the marginal portion of spacer;
This state of raising the marginal portion that keeps spacer is to make cell device; And with encapsulating material packaged battery element.Repeatedly finish stacking procedure by the step repeatedly, draw anode or negative electrode, draw spacer and keep drawing anode or negative electrode simultaneously, in the profile retaining member, insert anode or negative electrode and spacer, make the marginal portion of spacer be elevated, by discharge drawing anode or negative electrode and spacer, so that anode or negative electrode and spacer are installed together.
In a third aspect of the present invention, a kind of stack equipment is provided, be used to pile up anode, negative electrode and spacer, it comprises suction device and profile retaining member.Suction device comprises: electrode is drawn member, provides first vacuum mechanism, is drawn the marginal portion of anode at least or negative electrode by first vacuum mechanism; Spacer is drawn member, provides second vacuum mechanism, is drawn the marginal portion of spacer by second vacuum mechanism; And mobile member, be used for a lifting electrode and draw member and spacer absorption member.The profile retaining member is during piling up anode, negative electrode and spacer, by raising the marginal portion of spacer, the profile of holding anode, negative electrode and spacer.
Description of drawings
Figure 1A to 1C is used to illustrate the method for arranging of anode, negative electrode and spacer and the schematic diagram of problem thereof;
Fig. 2 is the sectional view that existing stacking nonaqueous electrolytes battery structure example is shown;
Fig. 3 is the sectional view that existing stacking nonaqueous electrolytes battery structure example is shown;
Fig. 4 is the sectional view that existing stacking nonaqueous electrolytes battery structure example is shown;
Fig. 5 A and 5B are the schematic diagrames that is shown specifically the stacking nonaqueous electrolytes battery structure shown in Fig. 3 and 4;
Fig. 6 A and 6B are the schematic diagrames that illustrates according to the example of the stacking nonaqueous electrolytes battery structure of the embodiment of the invention;
Fig. 7 A and 7B are the schematic diagrames that illustrates according to the battery element structure of the embodiment of the invention;
Fig. 8 illustrates according to the anode of the embodiment of the invention and the schematic diagram of cathode construction;
Fig. 9 A and 9B are the schematic diagrames that the suction device structure that is included in the stack equipment is shown, and this equipment is used to make the nonaqueous electrolyte battery according to the embodiment of the invention;
Figure 10 A and 10B illustrate the schematic diagram how suction device draws electrode and spacer;
Figure 11 A and 11B illustrate the sectional view that the suction device that is included in the stack equipment and profile retainer are arranged;
Figure 12 A to 12L is the schematic diagram that electrode and the stacked technology of spacer are shown;
Figure 13 A and 13B illustrate the schematic diagram that how electrode and spacer are provided with when electrode and spacer insert respectively;
Figure 14 A and 14B are used to illustrate the schematic diagram of granting the direction of vibration after piling up; With
Figure 15 is the schematic diagram that is used to illustrate by the observed planar section of CT.
Embodiment
Now with reference to accompanying drawing embodiments of the invention are described.
(1) structure of stacking nonaqueous electrolytes battery
Fig. 6 A shows the outward appearance according to the stacking nonaqueous electrolytes battery 10 of the embodiment of the invention, and Fig. 6 B shows the structure example of stacking nonaqueous electrolytes battery 10.In addition, Fig. 7 A shows the vertical view of the cell device 20 in the stacking nonaqueous electrolytes battery 10 of packing into, and Fig. 7 B shows along the a-a ' line of cell device 20 and cuts open the sectional view of getting.
Shown in Fig. 6 A and 6B, stacking nonaqueous electrolytes battery 10 is made by following step: cell device 20 is packed in the moisture-resistant gas stacked film 27 as encapsulating material, inject the electrolyte solution (not shown), and will be sealed around the marginal portion of the stacked film 27 of cell device 20 by welding then.Cell device 20 has anode terminal 25 and cathode terminal 26, and these electrode terminals extend out as lead-in wire from cell device 20, and is folded between the marginal portion of corresponding stacked film 27.Each anode terminal 25 and cathode terminal 26 can have two surfaces that are coated with resin streak, so that for example improve the bonding force to stacked film 27.For this resin streak, adopt the material that has fine bonding force with the metal of making electrode terminal, for example, sour modified polyethylene material.
For example, shown in Fig. 7 B,, construct the cell device 20 in the stacking nonaqueous electrolytes battery 10 of packing into by the thing as a result that piles up a plurality of anodes 21 and negative electrode 22 through spacer 23 and use the adhesive tape 24 as fixed component fixedly to pile up.The edge of each spacer 23 all is elevated, and adhesive tape 24 is set makes a plurality of spacers 23, and preferred two spacers 23 overlap each other along the edge of electrode slice.Adhesive tape 24 is arranged on for example three sides, these three sides be except the outlet side of extraction electrode terminal the electrode sidepiece and with respect to the electrode of electrode outlet side bottom.
Encapsulating material
Stacked film 27 has for example stepped construction, wherein stacks gradually adhesive layer, metal level and sealer.Adhesive layer is formed by polymer film, this polymer film welds together by heating or ultrasonic wave and another sheet, and this polymer film by for example polypropylene (PP), polyethylene (PE), cast polypropylene (castedpolypropylene, CPP), LLDPE (LLDPE) and low density polyethylene (LDPE) (LDPE) form.Metal level is formed by metal forming, and its mainly to act on be to prevent entering of moisture, oxygen and light, protect relevant inclusion.Metal forming can be made by for example aluminium (Al), and this is because it is very light, is ductile, and price is low, and good processing properties etc.Except that aluminium, other metal also can be used as metal forming.Sealer is made by for example nylon (Ny) or polyethylene terephthalate (PET), and this is because they have good outward appearance, toughness and flexibility etc.The surface of adhesive layer one side is to put the surface, is used for putting cell device 20 thereon.
The stacked film 27 of Xing Chenging has container part 27a like this, and it hollows out towards the sealer side from the adhesive layer side.By this container part 27a that cell device 20 is packed into, the sealing of cell device 20 can be improved.Container part 27a is by formation such as deep drawn.
Non-aqueous electrolytic solution
About non-aqueous electrolytic solution, can adopt normally used any electrolytic salt of nonaqueous electrolyte battery and organic solvent.
Specifically, nonaqueous solvents comprises ethylene carbonate (ethylenecarbonate, EC), propene carbonate (propylenecarbonate, PC), gamma-butyrolacton, dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), dipropyl carbonate (DPC), ethyl propyl carbonic acid ester (ethylpropylcarbonate, EPC), and with halogen atom replace the solvent that the hydrogen atom of these carbonate obtains.These solvents can use separately or be used in combination with predetermined composition.
In addition, any electrolytic salt that can adopt the non-aqueous electrolytic solution typical case to adopt.Specifically, it can comprise LiCl, LiBr, LiI, LiClO
3, LiClO
4, LiBF
4, LiPF
6, LiNO
3, LiN (CF
3SO
2)
2, LiN (C
2F
5SO
2)
2, LiAsF
6, LiCF
3SO
3, LiC (SO
2CF
3)
3, LiAlCl
4And LiSiF
6Yet, from the viewpoint of oxidation stability, LiPF
6And LiBF
4Be preferred.These lithium salts may be used singly or in combin.As long as lithium salts can be dissolved in any top solvent, it can dissolve under any concentration and no problem, and still preferred scope with respect to the nonaqueous solvents lithium concentration is 0.4mol/kg to 2.0mol/kg.
Cell device
To describe cell device 20 in detail below.
Anode
As shown in Figure 8, anode 21 comprises anode collector 21b and is formed on two lip-deep anode active material layers 21a of this anode collector 21b.Anode collector 21b is by for example Al paper tinsel manufacturing of metal forming.In addition, draw as lead-in wire from a side of anode 21 with the integrally formed anode terminal 25 of anode collector 21b.
Active material of positive electrode, conductive agent and adhesive form anode active material layers 21a by for example comprising.
About active material of positive electrode,, can adopt metal oxide, metal sulfide or specific polymer according to the battery types of hope.For example, for lithium ion battery, adopt mainly by Li
xMO
2Lithium-compound transition metal oxide that (M represents one or more transition metal, and x changes according to the charge/discharge condition of battery, and scope is 0.05 to 1.10 usually) forms.The transition metal of making lithium composite xoide comprises cobalt (Co), nickel (Ni) and/or manganese (Mn).
The instantiation of lithium composite xoide comprises LiCoO
2, LiNiO
2, LiMn
2O
4And LiNi
yCo
1-yO
2(0＜y＜1) etc.In addition, also can adopt by the part transition metal being replaced to the various solid solution that another kind of element obtains, wherein LiNi
0.5Co
0.5O
2And LiNi
0.8Co
0.2O
2Be some examples.These lithium composite xoides can produce high voltage, and fine on energy density.In addition, as other active material of positive electrode, can adopt the metal sulfide or the metal oxide that do not comprise lithium, for example TiS
2, MoS
2, NbSe
2And V
2O
5These active material of positive electrode may be used singly or in combin.
In addition, conductive agent comprises for example material with carbon element, as carbon black and graphite.Adhesive comprises for example polyvinylidene fluoride (PVdF) and polytetrafluoroethylene (PTFE).
Negative electrode
Cathode active material bed of material 22a by comprise active material of cathode for example, in case of necessity conductive agent and adhesive forms.
Active material of cathode comprises the material with carbon element of lithium metal, lithium alloy or the elements doped lithium that can mix/go, perhaps the composite material of being made by metal-containing material and carbonaceous material.Specifically, the material with carbon element of elements doped lithium of can mixing/go can comprise graphite, ungraphitised carbon and soft black (soft carbon).More particularly, can adopt material with carbon element, for example RESEARCH OF PYROCARBON (pyrolitic carbon), coke (pitch coke, needle coke, petroleum coke), graphite, vitreous carbon (glassy carbon), organic high molecular compound sintered body (organicpolymer-compound baked body) (under suitable temperature, obtaining), carbon fibre and active carbon by curing phenolic resins or furane resins etc. and they being carried out carbonization.In addition, the material of the elements doped lithium that can mix/go can comprise condensate, for example polyacetylene (polyacethylene) and polypyrrole, and as SnO
2Oxide.
In addition, the alloy material that has lithium comprises various metals, wherein can adopt tin (Sn), cobalt (Co), indium (In), aluminium (Al), silicon (Si) and their alloy.When adopting lithium metal, there is no need to adopt the lithium powder to form coated film, and what can substitute is the method for the lithium metal foil of the bonding roll extrusion of compression on collector with adhesive.
The adhesive that can adopt comprises for example polyvinylidene fluoride (PVdF) and styrene butadiene ribber (SBR) etc.
Spacer
Employing is than each the big spacer 23 of overall dimension of anode 21 and negative electrode 22, so that prevent the short circuit between anode 21 and negative electrode 22.The size of spacer 23 is suitably selected according to the size and the thickness of anode 21 and negative electrode 22, with the marginal portion that guarantees when spacer and anode 21 and negative electrode 22 are stacked 23 of at least two spacers marginal portion overlapping along electrode.
Usually, thickness range is that the spacer 23 of 5 μ m to 50 μ m is fit for services.Its thickness range is that 7 μ m to 30 μ m are more preferred.If spacer 23 is too thick, then the amount of the active material of being filled reduces, and this has reduced battery capacity, and has also reduced ionic conductivity, and this has reduced current characteristics.On the contrary, if spacer 23 is too thin, then the mechanical strength of film reduces.
Fixed component
In addition, fixed component is not limited to the adhesive tape 24 that formed by polypropylene (PP), low density polyethylene (LDPE) (LDPE), high density polyethylene (HDPE) (HDPE), polyethylene terephthalate (PET), PEN (PEN), polyphenylene sulfide (PPS) or polyimides (PI), but also can comprise any member, need only its anti-electrolytic solution and can keep stacked state.
(2) manufacture method of stacking nonaqueous electrolytes battery
Next, will method that make stacking nonaqueous electrolytes battery 10 according to embodiments of the invention be described.This manufacture method comprises the steps: by suction device anode 2 μ or negative electrode 22 and spacer 23 to be inserted in the profile retaining members, and this profile retaining member is stacked in electrode stack on the position of hope, and discharges the suction to electrode and spacer 23 together.These steps repeat several times, to pile up a plurality of electrodes.At first, use description to pile up the stack equipment of anode 21, negative electrode 22 and spacer 23.
Stack equipment
Fig. 9 A is the sectional view of suction device 30, and Fig. 9 B is the upward view of suction device 30.
Should be noted in the discussion above that electrode draws hole 31b and be provided at by anode 21 or negative electrode 22 in any on the position in the less zone that limits of overall dimension.As selection, electrode is drawn hole 31b and can be provided at electrode by suitable pipeline setting and draw the central portion of module 31 and grade on the part.Yet,, can draw electrode reliably by locating these holes to draw at least the mode of the peripheral part of electrode.
In addition, electrode absorption module 31 has for example groove 34.About this structure, even electrode draws module 31 and contact with electrode, and groove 34 also can exposed electrode, so is easy to follow-up use adhesive tape 24 fixed electrodes.
Spacer is drawn module 32 and is provided with in the mode of drawing module 31 around electrode, and has a plurality of spacers absorption hole 32b that are used to draw spacer 23 on its basal surface.Spacer absorption hole 32b is provided on the marginal portion that isolates on electrode absorption module 31 sides of drawing module 32, makes that spacer 23 is drawn, shown in Figure 10 B when being vacuumized by the Air Coupling 32a that is connected to pipeline from spacer absorption hole 32b.Spacer is drawn hole 32b and is arranged to draw module 31 than the more close electrode in spacer 23 marginal portions.
So the suction device 30 of structure is drawn electrode and spacers 23, and the profile retainer 35 that afterwards electrode and spacer 23 is inserted as the profile retaining member.At this moment, shown in Figure 11 A and 11B, suction device 30 and profile retainer 35 are arranged to not disturb each other.In addition, spacer is drawn module 32 and profile retainer 35 leaves groove 34 by being provided with, and structure makes that the bonding of adhesive tape 24 do not hindered.
Should be noted in the discussion above that in order to adopt above-mentioned suction device 30 and profile retainer 35 suitable stacked electrodes and spacers 23, the following consideration of optimum seeking site of the marginal portion of negative electrode 22 and spacer 23.
Thereby the size that negative electrode 22 is set has very little gap with respect to profile retainer 35, and this gap preferably sets the inside dimension with respect to profile retainer 35 to be not less than 0.1mm and to be not more than 0.2mm.Negative electrode 22 must increase its gap with respect to spacer 23 marginal portions with respect to the big gap of profile retainer 35, makes spacer 23 excessive with respect to negative electrode 22.This has reduced the volumetric efficiency of battery.In addition, when the gap becomes when too big, the problem that this can cause the spacer 23 adjacent to negative electrode 22 to be difficult to raise.Consider this point, be preferably the gap that minimizes between negative electrode 22 and the profile retainer 35.Yet, if the gap is too little, reduced the reception space of 23 of another spacers of raising from lower floor, therefore hinder the spacer marginal portion by suitable raising.
Gap between negative electrode 22 and the profile retainer 35 preferably is not less than 0.1mm.In order to make at least two 23 of spacers overlap each other, the spacer of general type should require the minimum clearance of 0.1mm, and this value equals 23 of two spacers and is used for the thickness sum in some gap of their insertion.
Spacer with higher function can require even littler gap, and this is because the thickness of spacer 23 defines desired gap.In the case, require during negative electrode 22 inserts, to improve positioning accuracy.
Preferably, profile retainer 35 makes its external dimensions edge with respect to the spacer 23 of correspondence on its side reduce to be no less than 0.4mm and be not more than 0.6mm; Promptly preferably, the inside dimension of profile retainer 35 is no less than 0.8mm and is not more than 1.2mm less than the external dimensions of spacer 23.The inside dimension that spacer 23 is greater than profile retainer 35 approximates the thickness of at least two spacer sheets, and the marginal portion of these two spacer sheets is elevated and overlaps one another along the marginal portion of electrode.If it is too big that spacer 23 becomes, then spacer 23 marginal portion of raising curves inwardly, make when inserting next electrode and spacer group, insert difficult.
In addition, the spacer of spacer absorption module 32 is drawn the hole and preferably is provided at the position that spacer 23 peripheries inwardly are not less than 0.05mm and are not more than 0.25mm.If less than 0.05mm, then becoming is difficult to adjust the position of spacer 23, can not draw spacer 23 thus.If more than 0.25mm, then the edge part branch of spacer 23 down, the marginal portion of spacer can not suitably be raised when spacer is inserted into profile retainer 35 thus.Here, the position of spacer absorption hole 23b is represented by the air line distance of drawing the perimeter of hole 32b from spacer 23 marginal portions to spacer.
The manufacturing of stacking nonaqueous electrolytes battery
Adopt aforesaid stack equipment, make stacking nonaqueous electrolytes battery 10 by stacked electrodes.At first, make anode 21 and negative electrode 22.
Make anode
The metal forming that is used for the material of anode collector 21b is stamped into the shape of requirement, to form anode collector 21b.At this moment, metal forming is stamped into such shape, makes anode terminal 25 as a slice side-prominent from anode collector 21b, and anode collector 21b and anode terminal 25 form a unit thus.
Above-mentioned active material of positive electrode, adhesive and conductive agent are uniformly mixed into anode mixture, and this anode mixture is distributed in the solvent to be prepared into slurry.Then, this slurry is coated on the anode collector 21b equably by The tape casting etc., the at high temperature dry afterwards solvent of removing.Therefore, form anode active layer 21a.Should be noted in the discussion above that N-N-methyl-2-2-pyrrolidone N-(NMP) etc. is as solvent.As long as active material of positive electrode, conductive agent, adhesive and the even dispersion of solvent all are acceptable, and regardless of their mixing ratio.
Make negative electrode
The metal forming that is used as above-mentioned cathode current collector 22b material is stamped into the shape of requirement, to form cathode current collector 22b.At this moment, cathode current collector 22b and cathode terminal 26 form a unit, are similar to the situation of anode collector 21b.
For example form by active material of cathode, conductive agent and adhesive in case of necessity by comprising for the cathode active material bed of material.They are mixed into cathode mix equably, and this cathode mix is dispersed in the solvent to make slurry.Then, this slurry is coated on the cathode current collector 22b equably by The tape casting etc., and at high temperature drying removes solvent afterwards.Therefore, form cathode active material bed of material 22a.Here, active material of cathode, conductive agent and adhesive can mix by any ratio, are similar to the situation of anode active material layers.
Make cell device
Next, make cell device 20 by piling up anode 21, negative electrode 22 and spacer 23.Pile up technology shown in Figure 12 A to 12L, wherein only schematically show the structure of suction device 30, and omitted some reference number.
At first, negative electrode 22 is drawn module 31 by electrode and is drawn (Figure 12 A).Then, suction device 30 is reduced by the lifting tube (not shown), so that negative electrode 22 is inserted profile retainer 35 (Figure 12 B), rises afterwards (Figure 12 C).Then, anode 21 is drawn module 31 by electrode and is drawn, and spacer 23 is drawn module 32 absorptions (Figure 12 D) by spacer.Suction device 30 descends, to pile up spacer 23 and anode 21 on negative electrode 22 (Figure 12 E) simultaneously.At this moment, the marginal portion of spacer 23 is raised by profile retainer 35.
Subsequently, suction device 30 rises (Figure 12 F), and negative electrode 22 draws module 31 by electrode and draw, and spacer 23 is drawn module 32 by spacer and drawn (Figure 12 G).Then, suction device 30 descends, to pile up spacer 23 and negative electrode 22 (Figure 12 H) simultaneously.At this moment, the marginal portion of the spacer 23 that piles up with negative electrode 22 is raised by profile retainer 35, and on each side along the marginal portion of negative electrode 22, overlap with the marginal portion of raising of the spacer 23 that piles up with anode 21.Rising suction device 30 backs (Figure 12 I) again, repeating the step of Figure 12 D to 12I, up to forming the stacked electrodes main body that requires.Should be noted in the discussion above that and carry out this lamination process, make anode terminal 25 overlap each other, and cathode terminal 26 overlaps each other.
In addition, after negative electrode 22 is stacked as the superiors' electrode layer, the groove 34 that adhesive tape 24 is drawn module 31 (not shown) exposed electrode at electrode is adhered to both sides and bottom, keeps suction device 30 to push the electrode that piles up simultaneously, with the electrode (Figure 12 J) that keeps and fixedly pile up.At last, suction device 30 rises (Figure 12 K), and takes out the electrode that piles up from profile retainer 35, the electrode body that piles up with formation.In this electrode body that piles up, by respectively a plurality of anode terminals 25 and anode 21 integral body being connected into a unit, and respectively a plurality of cathode terminals 26 are connected into a unit with negative electrode 22 integral body, form cell device 20 thus.
When drawing spacer 23, not only draw the vacsorb of module 32, and between electrode and spacer 23, set up static, and therefore can carry out stable absorption by spacer.
In addition, if possible, electrode that is stacked in advance and spacer 23 can be drawn module 31 and spacer by electrode and draw module 32 and draw together.
Make stacking nonaqueous electrolytes battery
The cell device 20 of Zhi Zaoing the putting among the part 27a of the stacked film 27 that forms by the deep drawn shown in Fig. 6 B of packing into as mentioned above.The stacked film 27 folding next openings that put part 27a that make are capped, and the both sides that put part 27a periphery then weld by for example heating etc.Subsequently, put part 27a and fill electrolyte solution, and this side is made stacking nonaqueous electrolytes battery 10, as shown in Figure 6A thus after this by the thermal weld sealing by a side of not welding as yet.Stacked film 27 can be the folded form shown in Fig. 6 B, and perhaps two 27 of stacked films can be used for from clamping cell device 20 up and down.
If electrode and spacer insert independent of one another, then spacer 23 can not suitably be raised, and as shown in FIG. 13A, and this causes that connecing down the negative electrode 22 that inserts is pressed on the marginal portion of spacer 23, shown in Figure 13 B, this has hindered a plurality of spacers 23 partly to overlap along each electrode edge.If adopt suction device 30, electrode and spacer 23 are stacked, thus spacer 23 suitably raised, made stacking nonaqueous electrolytes battery 10 thus according to present embodiment.
In the stacking nonaqueous electrolytes battery of making as mentioned above, each marginal portion of spacer is elevated, and a plurality of spacers overlap along each edge of electrode, prevent that thus electrode from departing from its suitable position, and prevent from further to strengthen the reliability of battery owing between electrode and spacer, entering short circuit and the suitably inefficacy of cell reaction that foreign matter causes.
In addition, twine the battery that piles up type etc. with normally used spiral and compare, can reduce the quantity of used spacer, and improve volumetric efficiency and reduce manufacturing cost, because do not need expensive spacer folding apparatus etc.
In addition, electrode and spacer can pile up by the technology that simple steps reduces, and have improved productive rate thus.
Example
Adopt above-mentioned stacking nonaqueous electrolytes battery, detected vibration resistance.In the example below.By preparing anode and negative electrode and thereafter they and spacer being stacked as shown in Figure 8, made the cell device shown in Fig. 7 A and the 7B.
＜example 1 〉
Make anode
By mixing the cobalt acid lithium (LiCoO of 92wt% equably
2), powdery polyvinylidene fluoride and the 5wt% powdered graphite of 3wt% prepare anode mixture, and this mixture is distributed to N-N-methyl-2-2-pyrrolidone N-(NMP), to make the anode mixture slurry.This anode mixture slurry is coated on two surfaces of aluminium (Al) paper tinsel that will become anode collector equably, 100 ℃ of following vacuumizes 24 hours, and thereafter by the roll unit compression forming, forms anode active material layers thus.
Make negative electrode
Prepare cathode mix by the Delanium and the 9wt% powdery polyvinylidene fluoride that mix 91wt% equably, and this mixture is scattered in N-N-methyl-2-2-pyrrolidone N-(NMP), to make the cathode mix slurry.This cathode mix slurry is coated on two surfaces of copper (Cu) paper tinsel that will become cathode current collector equably, and 120 ℃ of following vacuumizes 24 hours, and, form the cathode active material bed of material thus thereafter by the roll unit compression forming.The external dimensions that should be noted in the discussion above that negative electrode forms the external dimensions 2mm greater than anode.
The preparation electrolytic solution
LiPF by dissolving 0.8mol/kg in the solvent that mixes at 6: 4 with weight ratio at ethylene carbonate (EC) and propene carbonate (PC)
6LiBF with 0.2mol/kg
4Prepare electrolyte solution.
Make cell device
The stack equipment of employing shown in Figure 11 A and 11B piles up anode, negative electrode and spacer.The order that they pile up be ground floor negative electrode, spacer, ground floor anode, spacer, second layer negative electrode, spacer, second layer anode ..., the 15 layer of negative electrode, spacer, the 15 layer of anode, spacer, the 16 layer of negative electrode, and resulting sandwich is fixed by adhesive tape.Anode and negative electrode are stacked into and make the gap of 1mm is provided between the marginal portion on they every sides.Equally, between the inside dimension of cathode edge part and profile retainer, set the gap of 0.1mm.
＜example 2 〉
After piling up anode, negative electrode and spacer and fixedly piling up result product, on couch position and stand up position, pile up result product each five times, shown in Figure 14 A and 14B with hand moving.Cell device is similar to the situation of example 1 and makes, except piling up the after-applied vibration.
＜example 3 〉
After piling up first negative electrode to the, 13 negative electrodes, stack equipment is held in the hand, and is piling up the 16 KD liftings of the 13 anode to the.Except aforesaid operations, cell device is similar to the situation manufacturing of example 1.Should be noted in the discussion above that " during piling up " mean suction device draw electrode and spacer and drop to their stacked position during.
With X-ray CT (computed tomography) each example of the cell device of such manufacturing is made a video recording, the planar cross-sectional that P represents intersects X-axis along the sidepiece of a cell device, and the planar cross-sectional that Q represents intersects the Z axle along the bottom of a cell device, as shown in figure 15.Should be noted in the discussion above that in each sidepiece and bottom, on the position of one of distance bottom corner 15mm, cut open the face cross section of making even, and will observe these planar cross-sectional.
In the CT image that piles up planar cross-sectional on sidepiece and bottom, detected following point.
(a) maximum deviation of Cathode Foil
In the first to the 16 negative electrode, select two the maximum negative electrodes of distance between their marginal portion, and analyzed should distance.In this negative electrode, should be noted in the discussion above that by their marginal portion of considering to form of cathode current collector and analyze maximum deviation that this is can not pass through the CT image viewing because of the cathode active material bed of material as the position of the marginal portion of negative electrode by Cu.
(b) maximum deviation of anode foils
In the first to the 15 anode, select two the maximum anodes of distance between their marginal portion, and analyzed should distance.In this anode, should be noted in the discussion above that by the marginal portion of considering anode active material layers and analyze maximum deviation that this is can not pass through the CT image viewing because of the anode collector that is formed by Al as the position of the marginal portion of anode.
(c) anode adjacent one another are and the maximum deviation between the negative electrode
The centering of all anodes adjacent one another are and negative electrode, selected the distance between their marginal portion to be maximum an antianode and negative electrode, and analyzed should distance.For " anode adjacent one another are and negative electrode ", this for example be meant by the tenth negative electrode and the tenth anode or the tenth anode and the 11 negative electrode form any a pair of.When this distance equaled 1mm, this can think " not having deviation ", and this is because the gap of 1mm is provided between anode and negative electrode.In addition, the marginal portion that by the marginal portion of considering anode active material layers is the cathode current collector that formed by Cu of the position and considering of the marginal portion of anode is that maximum deviation is analyzed in the position of the marginal portion of negative electrode, and this is can not observe by the CT image because of the aforesaid anode collector and the cathode active material bed of material that is formed by the Al paper tinsel.
The result who analyzes is as shown in table 1 below.
[table 1]
Compare with the cell device that does not apply vibration according to example 1, according to example 2 and 3 stacked back or during apply in the electrode of cell device at them of vibration and demonstrate the deviation that equates basically.In addition, because the gap between cathode edge part and the profile retainer is that the gap between 0.1mm and anode edge part and the cathode edge part is 1mm, so should be understood that, in the cell device of making as the above embodiment of the present invention, even after stacked electrodes or during cell device is applied vibration, anode does not partly extend from cathode edge yet, has therefore avoided short circuit etc.
According to embodiments of the invention, fixed component provides and makes spacer raise, and a plurality of spacers of raising overlap each other along the marginal portion of anode or negative electrode, thereby can prevent that electrode from departing from its suitable position, and prevent that foreign matter from entering from the marginal portion of stacked body.
In addition, in an embodiment of the present invention, neither need water-tight equipment also not need special folding apparatus, thereby can make stacking nonaqueous electrolytes battery with simple technology for spacer.
According to embodiments of the invention, providing can be with simple technology manufacturing and the stacking nonaqueous electrolytes battery with fine quality and performance, and manufacture method and the stack equipment that is used for it is provided.
Although described the present invention above in detail, the invention is not restricted to the foregoing description, and can carry out modification on the various forms according to technological thought of the present invention.
For example, the numerical value of mentioning in the above-described embodiments only is an example, therefore can adopt different numerical value in case of necessity.
In addition, this stacking nonaqueous electrolytes battery can be used as primary cell or secondary cell, and not only can be encapsulated in the stacked film but also can be encapsulated in the battery can.
The application requires to be committed on February 19th, 2007 priority of Japanese patent application 2007-37974 number of Japan Patent office, and its full content is incorporated herein by reference.
Claims (22)
1. stacking nonaqueous electrolytes battery comprises:
A plurality of anodes and negative electrode alternately pile up and are isolated by spacer,
Wherein this spacer has the marginal portion of raising along the marginal portion of one of this anode and negative electrode, and this marginal portion of raising of a plurality of these spacers overlaps each other, and
The stacked electrodes main body of being made up of these a plurality of anodes and the negative electrode of this spacer isolation is fixed into the state that piles up by fixed component.
2. stacking nonaqueous electrolytes battery according to claim 1, wherein the overlapping of this of this spacer marginal portion of raising is formed by two or more marginal portions.
3. stacking nonaqueous electrolytes battery according to claim 1, wherein this negative electrode comprises the cathode current collector and the cathode active material bed of material, the external dimensions of this cathode current collector is greater than the external dimensions of anode collector, and this cathode active material bed of material is formed on two surfaces of this cathode current collector.
4. stacking nonaqueous electrolytes battery according to claim 1, wherein this fixed component is provided on three sides, this three side be except the electrode outlet side the electrode sidepiece and with respect to the electrode of this electrode outlet side bottom.
5. stacking nonaqueous electrolytes battery according to claim 1, wherein this fixed component is an adhesive tape.
6. method of making stacking nonaqueous electrolytes battery, this stacking nonaqueous electrolytes battery comprise a plurality of anode and negative electrodes that alternately pile up and isolated by spacer, and this method comprises the steps:
Pile up this spacer and this anode or negative electrode, make the marginal portion of this spacer raise;
The state that keeps this marginal portion of raising of this spacer is to make cell device; And
Encapsulate this cell device with encapsulating material;
Wherein repeatedly carry out this stacking procedure by repeating following step:
Draw this anode or negative electrode;
The absorption of drawing this spacer and keeping this anode or negative electrode;
In this anode or negative electrode and this spacer insertion profile retaining member, make this marginal portion of this spacer raise; And
By discharging the absorption of this anode or negative electrode and this spacer, this anode or negative electrode are installed are in the same place with this spacer.
7. the method for manufacturing stacking nonaqueous electrolytes battery according to claim 6, wherein this marginal portion of this spacer remains the state of raising by fixed component, and this fixed component is used for the stacked electrodes main body be made up of these a plurality of anodes that alternately pile up and isolated by this spacer and negative electrode.
8. the method for manufacturing stacking nonaqueous electrolytes battery according to claim 6, wherein this anode, this negative electrode and this spacer are by vacsorb.
9. the method for manufacturing stacking nonaqueous electrolytes battery according to claim 6, wherein this marginal portion of this spacer is lifted, and a plurality of this marginal portion overlaps in this marginal portion of this anode or negative electrode.
10. the method for manufacturing stacking nonaqueous electrolytes battery according to claim 9, wherein these a plurality of marginal portions are formed by two marginal portions.
11. a stack equipment that piles up anode, negative electrode and spacer comprises:
Suction device comprises:
Electrode is drawn member, provides first vacuum mechanism, is drawn the peripheral part of this anode or negative electrode at least by this first vacuum mechanism;
Spacer is drawn member, provides second vacuum mechanism, is drawn the peripheral part of this spacer by this second vacuum mechanism; And
Mobile member is used for raising together or reduces that this electrode is drawn member and this spacer is drawn member; And
The profile retaining member is used for by raising the marginal portion of this spacer, keeping the profile of this anode, this negative electrode and this spacer during the piling up of this anode, this negative electrode and this spacer.
12. stack equipment according to claim 11, wherein this spacer is drawn the static that produces between this second vacuum mechanism of member and this anode or the negative electrode by this spacer and is drawn.
13. stack equipment according to claim 11, wherein this first vacuum mechanism is drawn this anode or negative electrode by the absorption hole in the electrode absorption surface that is provided at this electrode absorption member.
14. stack equipment according to claim 13, wherein this electrode absorption member has this absorption hole, to draw this peripheral part of this anode or negative electrode at least.
15. stack equipment according to claim 11, wherein this second vacuum mechanism is drawn this spacer by the absorption hole in the spacer absorption surface that is provided at this spacer absorption member.
16. stack equipment according to claim 13, wherein this spacer absorption member has this absorption hole that is provided at wherein, to draw this peripheral part of this spacer.
17. stack equipment according to claim 13, wherein this absorption hole is provided at and is not less than 0.05mm within the marginal portion of this spacer and is not more than on the position of 0.25mm.
18. stack equipment according to claim 13, wherein this spacer absorption member and this profile retaining member are provided as each other and do not interfere.
19. stack equipment according to claim 11, wherein this profile retaining member forms the external dimensions of its inside dimension less than this spacer.
20. stack equipment according to claim 11, wherein this profile retaining member forms its inside dimension and is no less than 0.8mm and is not more than 1.2mm less than this external dimensions of this spacer.
21. stack equipment according to claim 11 wherein provides the gap between this negative electrode and this profile retaining member.
22. stack equipment according to claim 21, wherein this gap is not less than 0.1mm and is not more than 0.2mm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP037974/07 | 2007-02-19 | ||
| JP2007037974A JP4293247B2 (en) | 2007-02-19 | 2007-02-19 | Multilayer nonaqueous electrolyte battery and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101252208A CN101252208A (en) | 2008-08-27 |
| CN101252208B true CN101252208B (en) | 2010-06-09 |
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| CN2008100804820A Active CN101252208B (en) | 2007-02-19 | 2008-02-19 | Stacking nonaqueous electrolytes battery and manufacturing method thereof and stacking equipment |
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| Country | Link |
|---|---|
| US (1) | US8765307B2 (en) |
| JP (1) | JP4293247B2 (en) |
| CN (1) | CN101252208B (en) |
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| CN101252208A (en) | 2008-08-27 |
| JP2008204706A (en) | 2008-09-04 |
| US8765307B2 (en) | 2014-07-01 |
| JP4293247B2 (en) | 2009-07-08 |
| US20080305398A1 (en) | 2008-12-11 |
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